EP4304409A1 - Strobel pour un article chaussant, article chaussant et procédé de fabrication de l'article chaussant - Google Patents

Strobel pour un article chaussant, article chaussant et procédé de fabrication de l'article chaussant

Info

Publication number
EP4304409A1
EP4304409A1 EP22711529.2A EP22711529A EP4304409A1 EP 4304409 A1 EP4304409 A1 EP 4304409A1 EP 22711529 A EP22711529 A EP 22711529A EP 4304409 A1 EP4304409 A1 EP 4304409A1
Authority
EP
European Patent Office
Prior art keywords
strobel
etpu
footwear
article
hybrid material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22711529.2A
Other languages
German (de)
English (en)
Inventor
Zhi Hui Liu
Wahju ARDIANTO
Yoke Khim Raymond Toh
Kai Liu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP4304409A1 publication Critical patent/EP4304409A1/fr
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/38—Built-in insoles joined to uppers during the manufacturing process, e.g. structural insoles; Insoles glued to shoes during the manufacturing process
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • A43B17/003—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined characterised by the material
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • A43B17/14—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined made of sponge, rubber, or plastic materials
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
    • A43D86/00—Machines for assembling soles or heels onto uppers, not provided for in groups A43D25/00 - A43D83/00, e.g. by welding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/35—Composite foams, i.e. continuous macromolecular foams containing discontinuous cellular particles or fragments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/08—Polyurethanes from polyethers

Definitions

  • Strobel for an article of footwear an article of footwear and process for manufacturing the article of footwear
  • the invention relates to footwear and more particularly to a strobel for an article of footwear, an article of footwear comprising the strobel and also the process for manufacturing the article of footwear.
  • Footwear construction commonly includes a strobel board, which is disposed at the bottom of the upper for closing the upper.
  • the strobel enables lasting of the upper and maintains the shape of the upper; ideally the strobel does not stretch and distort appreciably.
  • it often requires rigidity and may be made of typically textiles (non-wovens, wovens, knit) or papers. All of these materials have shortcoming of poor cushioning.
  • further layer(s), manufactured from soft foam may be lami nated or cemented to the proximal surface of the strobel to provide certain cushioning and com fort.
  • US 2016/0302517 A1 discloses a sole assembly having an outsole and a midsole disposed be low a strobel board, and also a topsole and an inner sole disposed above the strobel board; wherein the strobel board was made of non-wovens, wovens or knit.
  • WO 2020/112301 A1 describes a strobel of a relatively inelastic material provided with through holes, which could have overcome the negative effect of strobel on the cushioning and com pression characteristics of an underlying sole structure.
  • WO 2019231882 A1 discloses a strobel with two layers, the first of which is made of a relatively soft textile and the second is made of materials that inhibit a flowable polymeric material from penetrating the second layer.
  • the strobel In the preparation of footwear, the strobel is usually stitched to the upper. However, it is difficult to achieve a strong stitching between strobel made of foams and the upper, since the foam strobel usually has an insufficient strength to undergo the threading forces of the stitching line. For the above reasons, foams generally may not be used as materials for strobel.
  • the existing strobel (which is made of typically non-wovens, wovens, knit or papers) is often cemented to the outsole using adhesives, which requires an undesirable adhesion step in the preparation process of the footwear and is environmentally unfriendly.
  • the present invention provides a strobel for an article of footwear, wherein the strobel compris es ETPU.
  • the present invention further provides a strobel for an article of footwear, wherein the strobel comprises a hybrid material of ETPU and a PU foam matrix.
  • the present invention further provides an article of footwear comprising the strobel as defined in the above.
  • the present invention further provides a process of manufacturing an article of footwear, com prising: i) stitching an upper to the strobel as defined in the above; and/or ii) hot-pressing the strobel as defined in the above to an outsole.
  • Figure 1 shows an embodiment of the strobel according to the invention which comprises ETPU.
  • Figure 2 shows an embodiment of the strobel according to the invention which comprises a hy brid material of ETPU and a PU foam matrix.
  • the present invention provides a strobel for an article of footwear, wherein the strobel compris es ETPU or a hybrid material of ETPU and a PU foam matrix.
  • the strobel for an article of footwear may define any configurations.
  • the strobel consists of one layer of ETPU or a hybrid material of ETPU and a PU foam matrix. More prefer ably, the strobel comprises one layer of ETPU or a hybrid material of ETPU and a PU foam ma trix, and one layer of thin textile provided on the proximal surface of the hybrid material layer.
  • EPU expanded thermoplastic polyurethane
  • PU refers to polyurethane
  • the present invention provides a strobel for an article of footwear, wherein the strobel compris es ETPU.
  • Thermoplastic polyurethane (TPU) is prepared, for example, by reacting isocyanates with com pounds which are reactive toward isocyanates and have a molecular weight of from 500 to 10 000 g/mol and, if appropriate, chain extenders having a molecular weight of from 50 to 499 g/mol, if appropriate in the presence of catalysts and/or customary auxiliaries and/or additives, such as blowing agent.
  • the expanded thermoplastic polyurethanes (ETPU) are preferably obtained by expansion of the above-mentioned thermoplastic polyurethane particles, for exam ple when the TPU pellets are depressurized at temperatures above the softening temperature of the TPU in suspension process.
  • the ETPU is based on thermoplastic polyurethane produced by using poly ester polyalcohol, polyether polyalcohol, more preferably polytetrahydrofuran.
  • the polytetrahydrofuran used has a molecular weight of from 600 to 2500 g/mol, preferably 800- 2000 g/mol, more preferably 1000-1800 g/mol.
  • the polyester polyalcohol is preferably polyester diol, preferably one based on adipic acid and 1,4-butanediol, having a number average molecular weight of from 500 to 2500 g/mol, particularly preferably from 600 g/mol to 900 g/mol.
  • ETPU is described, for example, in patent applications US 20100047550 A1 or W02007/082838, which are incorporated herein to an extent that they do not conflict with the disclosure of the present application.
  • the strobel comprising ETPU may be produced by steamchest molding process or by heat press process, wherein these processes themselves are known by those skilled in the art.
  • the ETPU beads are charged into a proper-size strobel-shape mold, and then steamchest molded by introducing a steam with a temperatures of, for example 100°C to 140°C, preferably 110°C to 130°C; with the proviso that the specific ETPU beads optionally further expand, and fuse to one another to give a molding ETPU foam of strobel.
  • the ETPU beads fuse to one another in a closed mold with exposure to heat at a temperature of, for example, 100°C to 140°C, preferably 110°C to 130°C.
  • the mold is filled with the beads, then closed, and supplied with steam or hot air.
  • the ETPU beads optionally further expand, and fuse to one another to give a molding ETPU foam.
  • the foam may be semifinished product, for example sheet, profile, or finished molding with simple or complicated geometry and the strobel is obtained by cutting the molding foam to a strobel-shape.
  • the molding ETPU foam (i.e., the material directly used as the strobel) has a density of 50-500 kg/m 3 , preferably 70-400 kg/m 3 , more preferably 100-300 kg/m 3 , and most preferably 150-260 kg/m 3 , and even more preferably 200-250 kg/m 3 .
  • the ETPU bead is preferably spherical, elliptical, triangle or polygonal, or any other regular or irregular geometries.
  • ETPU has an average particle size of from 1 mm to 12 mm, preferably from 2 mm to 10 mm, more preferably from 3 mm to 8 mm, and even more preferably 3 mm to 7 mm.
  • an average particle size refers to an average diameter of the ETPU; in the case of non-spherical particles, for example elliptical particles, the diameter refers to the longest axis of the ETPU bead.
  • the molding ETPU foam has a hardness of 25-50 AskerC, preferably 25-45 AskerC, and more preferably 28-40 AskerC, measured according to JIS K 7312.
  • the molding ETPU foam has a rebound resilience of 50-80%, preferably 53- 75%, more preferably 55-70%, even more preferably 58-65%, measured according to DIN 53 512:2000.
  • ETPU is commercially available from BASF SE, for example under the tradename of InfinergyTM.
  • InfinergyTM is commercially available from BASF SE, for example under the tradename of InfinergyTM.
  • Other detailed information for InfinergyTM is described, for exam ple, in patent application US 20100047550 A1, which is incorporated herein to an extent that it does not conflict with the disclosure of the present application.
  • Strobel comprising hybrid material of ETPU and a PU foam matrix
  • the present invention further provides a strobel for an article of footwear, wherein the strobel comprises a hybrid material of ETPU and a PU foam matrix.
  • ETPU present in the hybrid material is as defined in the above.
  • the PU foam matrix has a density of 50-600 kg/m 3 , preferably 80-500 kg/m 3 , more preferably 100-400 kg/m 3 , even more preferably 150-300 kg/m 3 .
  • the PU foam matrix has cells of any shapes, preferably spherical, elliptical, triangle or polygonal, or any other regular or irregular geometries.
  • the hybrid material has a density of 50-600 kg/m 3 , preferably 100-500 kg/m 3 , more preferably 150-400 kg/m 3 , even more preferably 200-300 kg/m 3 .
  • the hybrid material has a hardness of 25-50 AskerC, preferably 25-45 Ask erC, and more preferably 30-43 AskerC, measured according to JIS K 7312.
  • the hybrid material has a rebound resilience of 30-80%, preferably 40-70%, more preferably 45-65%, and even more preferably 50-65%, measured according to DIN 53 512:2000.
  • the strobel comprising a hybrid material of ETPU and a PU foam matrix is produced by mixing (a) polyisocyanates with (b) compounds having hydrogena- toms which are reactive toward isocyanates, (c) expanded thermoplastic polyurethane (ETPU) particles and, if appropriate, (d) chain extenders and/or crosslinkers, (e) catalysts, (f) blowing agents and (g) further additives, and reacting the mixture in a mold to form the strobel compris ing the hybrid material.
  • ETPU expanded thermoplastic polyurethane
  • component (c) is as defined in the above.
  • Components (a), (b) and (d)-(g) have the same meanings as defined in the patent application US 20100047550 A1, which is incorporated herein to an extent that it does not conflict with the disclosure of the present application.
  • the organic and/or modified polyisocyanates (a) used to produce the polyurethane (PU) of the invention comprise the aliphatic, cycloaliphatic, and aromatic di- or poly-functional isocyanates known from the prior art (constituent a-1), and also any desired mixtures thereof.
  • diphenylmethane 4,4'-diisocyanate diphenylmethane 2,4'-diisocyanate
  • the mixtures of mono meric diphenylmethane diisocyanates with diphenylmethane-diisocyanate homologs having a relatively large number of rings polymer-MDI
  • tetramethylene diisocyanate tetramethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TDI 2,4- or 2,6-diisocyanate
  • the 4,4'-MDI preferably used can comprise from 0 to 20 wt.% of 2,4'-MDI and small amounts, up to about 10 wt.%, of allophanate- or uretonimine-modified poly isocyanates. It is also possible to use small amounts of polyphenylene polymethylene polyiso cyanate (polymeric MDI). The total amount of these high-functionality polyisocyanates should not exceed 5 wt.% of the isocyanate used.
  • Polyisocyanate component (a) is preferably used in the form of polyisocyanate prepolymers.
  • These polyisocyanate prepolymers are obtainable by reacting polyisocyanates (a-1) described above with polyols (a-2) to give the prepolymer, for example at temperatures of from 30 to 100°C, preferably at about 80°C.
  • Polyols (a-2) are known to those skilled in the art and are described by way of example in "Kun- ststoffhandbuch [Plastics handbook], Volume 7, Polyurethane [Polyurethanes]", Carl Hanser Verlag, 3rd Edition 1993, chapter 3.1.
  • Prepolymers based on ethers are preferably obtained by reacting polyisocyanates (a-1), particu larly preferably 4,4'-MDI, with 2- to 3-functional polyoxypropylene polyols and/or polyoxypropyl- ene-polyoxyethylene polyols. They are usually prepared by the generally known base-catalyzed addition of propylene oxide alone or in admixture with ethylene oxide onto H-functional, in par ticular OH-functional, starter substances. Starter substances employed are, for example, water, ethylene glycol or propylene glycol and also glycerol or trimethylolpropane. Furthermore, multi metal cyanide compounds, known as DMC catalysts, can also be used as catalysts. For exam ple, polyethers as described below under (b) can be used as component (a-2).
  • the ethylene oxide is preferably used in an amount of 10-50 wt.%, based on the total amount of alkylene oxide.
  • the alkylene oxides can be incorporated blockwise or as a random mixture. Particular preference is given to incor poration of an ethylene oxide end block (“EO cap”) in order to increase the content of more re active primary OH end groups.
  • EO cap ethylene oxide end block
  • the number average molecular weight of the polyols (a-2) is preferably in the range from 1750 to 5500 g/mol.
  • customary chain extenders or crosslinkers are added to the polyols mentioned in the preparation of the isocyanate prepolymers. Such substances are described below under c). Particular preference is given to using dipropylene glycol, tripropylene glycol or monoethylene glycol (MEG) as chain extenders or crosslinkers.
  • dipropylene glycol, tripropylene glycol or monoethylene glycol (MEG) as chain extenders or crosslinkers.
  • polyisocyanate component (a), preferably in the form of prepolymer, is used in an amount of from 30 to 50 wt.%, preferably from 35 to 45 wt.%, and in particular from 38 to 42 wt.%, based on the weight of components (a), (b) and (d)-(g).
  • Relatively high molecular weight component (b) having at least two H atoms which are reactive toward isocyanate is used.
  • Suitable component (b) may be selected from polyols, including pol- yetherols, polyesterols or mixtures thereof.
  • Polyetherols are prepared by known processes, for example via anionic polymerization using, as catalysts, alkali metal hydroxides or alkali metal alcoholates, and with addition of at least one starter molecule which comprises from 2 to 3 reactive hydrogen atoms, or via cationic polymeri zation using Lewis acids, such as antimony pentachloride or boron fluoride etherate, from one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical.
  • suitable alkylene oxides are tetrahydrofuran, propylene 1,3-oxide, butylene 1,2-oxide, butylene 2,3-oxide, and preferably ethylene oxide and propylene 1,2-oxide.
  • DMC catalysts multimetal cyanide compounds
  • the alkylene oxides can be used individually, in alternating succession, or in the form of a mixture. It is preferable to use mixtures composed of propylene 1 ,2-oxide and ethylene oxide, where the amounts of ethylene oxide used as ethylene oxide end block (EO cap) are from 10 to 50%, giving the resultant poly ols more than 70% of primary OH end groups.
  • EO cap ethylene oxide end block
  • the starter molecule used can comprise water or di- and tri-hydric alcohols, such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol, or trimethylolpropane.
  • the polyether polyols preferably polyoxypropylene-polyoxyethylene polyols, have a functionali ty of from 2 to 3 and a molecular weight of from 1000 to 8000 g/mol, preferably from 2000 to 6000 g/mol.
  • polyetherols obtained by ring-opening polymerization of tetrahydrofu ran preferably have a functionality of about 2 and have a number average molecular weight in the range from 500 to 4000 g/mol, preferably in the range from 700 to 3000 g/mol and more preferably in the range from 900 to 2500 g/mol.
  • Polytetrahydrofuran (PTHF) is also known in the pertinent art under the designations tetramethylene glycol (PTMG), polytetramethylene glycol ether (PTMEG) or polytetramethylene oxides (PTMO).
  • polyester polyols can be prepared from organic dicarboxylic acids having from 2 to 12 carbon atoms, preferably from aliphatic dicarboxylic acids having from 4 to 6 car bon atoms, and from polyhydric alcohols, preferably diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms.
  • dicarboxylic acids that can be used are: suc cinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
  • dicar boxylic acids here can be used either individually or else in a mixture with one another.
  • the free dicarboxylic acids it is also possible to use the corresponding dicarboxylic acid de rivatives, e.g. dicarboxylic esters of alcohols having from 1 to 4 carbon atoms, or dicarboxylic anhydrides.
  • dicarboxylic acid mixtures composed of succinic, glutaric, and adipic acid in quantitative proportions of, for example, 20-35 : 35-50 : 20-32 parts by weight, and in particular adipic acid.
  • di- and polyhydric alcohols in particular diols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerol, and trimethylolpropane. It is preferable to use ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. It is also possible to use polyester polyols derived from lactones, e.g. caprolactone, or hydroxycar- boxylic acids, e.g. hydroxycaproic acid.
  • lactones e.g. caprolactone
  • hydroxycar- boxylic acids e.g. hydroxycaproic acid.
  • the organic, e.g. aromatic, and preferably aliphatic, polycarboxylic acids and/or their derivatives and polyhydric alcohols can be polycondensed without a catalyst or preferably in the presence of esterification catalysts, advantageously in an atmosphere composed of inert gas, for example nitrogen, carbon monoxide, helium, argon, etc., in the melt at temperatures which are from 150 to 250°C, preferably from 180 to 220°C, if ap intestinalte at reduced pressure, until the desired acid number has been reached, this preferably being smaller than 10, particularly preferably smaller than 2.
  • inert gas for example nitrogen, carbon monoxide, helium, argon, etc.
  • the esterification mixture is polycondensed at the abovementioned temperatures until the acid number is from 80 to 30, preferably from 40 to 30, at atmospheric pressure, and then at a pressure which is smaller than 500 mbar, preferably from 50 to 150 mbar.
  • esterifi cation catalysts that can be used are iron catalysts, cadmium catalysts, cobalt catalysts, lead catalysts, zinc catalysts, antimony catalysts, magnesium catalysts, titanium catalysts, and tin catalysts, in the form of metals, of metal oxides, or of metal salts.
  • the polycondensa tion process can also be carried out in a liquid phase in the presence of diluents and/or entrain- ers, e.g. benzene, toluene, xylene, or chlorobenzene, for the azeotropic removal of the water of condensation by distillation.
  • diluents and/or entrain- ers e.g. benzene, toluene, xylene, or chlorobenzene
  • the polyester polyols are advantageously produced by polycon- densing the organic polycarboxylic acids and/or polycarboxylic acid derivatives and polyhydric alcohols in a molar ratio of 1:1 to 1.8, preferably 1:1.05 to 1.2.
  • the resultant polyester polyols preferably have a functionality of from 2 to 4, in particular from 2 to 3, and a molecular weight of from 480 to 3000 g/mol, preferably from 1000 to 3000 g/mol.
  • Mixtures comprising polyetherols and polyesterols are also suitable component (b).
  • polystyrene resins are polymer-modified polyols, preferably polymer-modified polyesterols or polyetherols, particularly preferably graft polyetherols or graft polyesterols, in particular graft polyetherols.
  • polymer polyol usually having from 5 to 60 wt.%, preferably from 10 to 55 wt.%, particularly preferably from 30 to 55 wt.%, and in particular from 40 to 50 wt.%, content of preferably thermoplastic polymers.
  • polyesterols are described by way of example in WO 05/098763 and EP-A 250 351, and are usually prepared via free-radical polymerization of suitable olefinic monomers, such as styrene, acrylonitrile, (meth)acrylates, (meth)acrylic acid, and/or acrylamide, in a polyesterol serving as graft base.
  • suitable olefinic monomers such as styrene, acrylonitrile, (meth)acrylates, (meth)acrylic acid, and/or acrylamide
  • the side chains are generally produced via transfer of the free radicals from growing polymer chains to polyesterols or polyetherols.
  • the polymer polyol comprises, alongside the graft copol ymer, mainly the homopolymers of the olefins, dispersed in unaltered polyesterol or polyetherol.
  • the monomers used comprise acrylonitrile, styrene, or acryloni trile and styrene, particularly preferably exclusively styrene.
  • the monomers are, if appropriate, polymerized in the presence of further monomers, of a macromer, and of a moderator, and with use of a free-radical initiator, mostly azo compounds or peroxide compounds, in a polyesterol or polyetherol as continuous phase. This process is described by way of example in DE 111 394, US 3304273, US 3383351, US 3523093, DE 1 152 536, and DE 1 152 537.
  • component (b) of suitable polyols are used in an amount of from 35 to 75 wt.%, preferably from 40 to 70 wt.%, and more preferably from 45 to 65 wt.%, and in particular from 50 to 60 wt.%, based on the weight of components (a), (b) and (d)-(g).
  • the hybrid materials of the invention can be produced with or without concomitant use of (d) chain extenders and/or crosslinking agents.
  • chain extenders, crosslinking agents or, if appropriate, else a mixture thereof can prove advantageous for modification of me chanical properties, e.g. of hardness.
  • These chain extenders and/or crosslinking agents are substances with a molar mass which is preferably smaller than 400 g/mol, particularly preferably from 60 to 400 g/mol, and chain extenders here have 2 hydrogen atoms reactive toward isocya nates while crosslinking agents have 3 hydrogen atoms reactive toward isocyanate. These can be used individually or in the form of a mixture.
  • diols and/or triols with mo lecular weights smaller than 400, particularly preferably from 60 to 300, and more particularly from 60 to 150.
  • examples of those that can be used are aliphatic, cycloaliphatic, and/or arali- phatic diols having from 2 to 14, preferably from 2 to 10, carbon atoms, e.g.
  • chain extenders, crosslinking agents, or a mixture of these are used, their amounts advanta geously used are from 1 to 60 wt.%, preferably from 1.5 to 50 wt.%, and in particular from 2 to 40 wt.%, based on the weight of components (b) and (d).
  • catalysts (e) are used for producing the hybrid materials of the invention, it is preferable to use compounds which markedly accelerate the reaction of the compounds of component (b) and, if appropriate, (d) comprising hydroxy groups with the organic, if appropriate modified, polyisocy anates (a).
  • amidines such as 2,3-dimethyl-3,4,5,6- tetrahydropyrimidine
  • tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl-, or N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine, pentamethyldiethy- lenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1 azabicyclo[3.3.0]octane, and preferably 1,4-diazabicyclo[2.2.2]octane, and alkanolamine
  • Organometallic compounds can also be used, preferably organotin compounds, such as stannous salts of organic carboxylic acids, e.g. stan nous acetate, stannous octoate, stannous ethylhexoate, and stannous laurate, and the dial- kyltin(IV) salts of organic carboxylic acids, e.g.
  • the organome tallic compounds can be used alone or preferably in combination with strongly basic amines. If component (b) involves an ester, it is preferable to use exclusively amine catalysts.
  • Blowing agents (f) are also present as matrix material during the production of polyurethane foams. These blowing agents comprise water where appropriate. Blowing agents (f) that can be used are not only water but also well-known compounds having chemical and/or physical action. Chemical blowing agents are compounds which form gaseous products via reaction with isocy anate, an example being formic acid. Physical blowing agents are compounds which have been dissolved or emulsified within the starting materials for polyurethane production and which va porize under the conditions of polyurethane formation. By way of example, these are hydrocar bons, halogenated hydrocarbons, and other compounds, e.g.
  • the blowing agent used comprises a mixture of said blowing agents, comprising water, and in particular is water as sole blowing agent. If no water is used as blowing agent, it is preferable to use exclusively physical blowing agents.
  • the content of water as blowing agent in one preferred embodiment is from 0.1 to 2 wt.%, pref erably from 0.2 to 1.5 wt.%, particularly preferably from 0.3 to 1.2 wt.%, more particularly from 0.4 to 1 wt.%, based on the total weight of components (b) and (f).
  • Auxiliaries and/or additives (g) can, if appropriate, also be added to the reaction mixture for pro duction of the hybrid materials of the invention.
  • Examples that may be mentioned are surfac tants, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis stabi lizers, odor-absorbent substances, and fungistatic and bacteriostatic substances.
  • the inorganic and organic fillers can be used individually or in the form of a mixture, and the amounts of these advantageously added to the reaction mixture are from 0.5 to 50 wt.%, pref erably from 1 to 40 wt.%, based on the weight of components (a), (b) and (d)-(g), where the content of matts, nonwovens, and textiles made of natural and synthetic fibers can, however, reach values up to 55 wt.%.
  • ETPU is present in an amount of 0.1-99 wt.%, preferably 30-90 wt.%, more preferably 40-80 wt.%, and even more preferably 45-60 wt.%, based on the total weight of the hybrid material.
  • component (b) Other substance suitable for using as component (b) is water. It is known to those skilled in the art that water may also be regarded as substance having hydrogen atom which is reactive to ward isocyanates, thus making it possible to act as component (b) in the production of polyure thane. In the case of water being used as component (b), additional blowing agents are not necessary.
  • components (a), (c)-(e) and (g) are the same as described in the above in terms of the material type.
  • components (a), (c)-(e) and (g) as described in the embodiments comprising polyol as component (b) also apply to the embodiments comprising water as component (b).
  • component (b) of water is used in an amount of from 0.5 to 5 wt.%, preferably from 0.8 to 4 wt.%, more preferably from 1 to 3 wt.%, based on the weight of components (a)- (b), (d)-(e) and (g).
  • component (a) is used in an amount of from 30-99 wt.%, preferably from 35-98 wt.%, more preferably from 45-97.5 wt.%, based on the weight of compo nents (a)-(b), (d)-(e) and (g). If component (d) is used, the amount advantageously used is from 1 to 5 wt.%, preferably from 2 to 4 wt.%, based on the weight of components (a)-(b), (d)-(e) and (g).
  • auxiliaries and/or additives (g) can, if present, be used individually or in the form of a mixture, and the amounts of these advanta geously added to the reaction mixture are from 0.5 to 50 wt.%, preferably from 1 to 40 wt.%, based on the weight of components (a)-(b), (d)-(e) and (g), where the content of matts, nonwovens, and textiles made of natural and synthetic fibers can, however, reach values up to 55 wt.%.
  • ETPU is present in an amount of 0.1-99 wt.%, preferably 40-98 wt.%, and more preferably 60-95 wt.%, based on the total weight of the hybrid material.
  • conductive particle may be added as a filler to the ETPU and/or PU foam matrix, in order to give a strobel with a good antistatic property.
  • the ETPU and a hybrid of ETPU and a PU foam matrix with conductive particles have relatively good electrostat ic discharge (ESD) properties.
  • the ETPU and a hybrid of ETPU and a PU foam matrix with conductive particles have comparable ESD properties with paper strobel.
  • the ETPU and a hybrid of ETPU and a PU foam matrix with conductive particles have a resistivity of > 10 7 Q m, preferably > 10 8 Q m, more preferably from 5 x 10 8 Q m to 5 x 10 10 Q m, and even more preferably from 5 x 10 8 Q m to 2 x 10 10 Q m.
  • the foams of hybrid material are preferably produced by the one-shot process by means of the low-pressure or high-pressure technique in closed, advantageously heated molds.
  • the molds usually comprise metal, e.g. aluminum or steel.
  • the starting components are for this purpose mixed at a temperature of from 15°C to 90°C, preferably from 20°C to 45°C, more preferably from 30°C to 40°C, and introduced into the closed mold, if appropriate under superatmospheric pressure, wherein the starting components include but are not limited to components (a)-(g).
  • Mixing can be carried out mechanically by means of a stirrer or a stirring screw or under high pressure in the countercurrent injection pro cess.
  • the mold temperature is advantageously from 20°C to 90°C, preferably from 30°C to 60°C.
  • proximal surface refers to the surface of the strobel board, outsole, insole (also referred to as “inner sole”, “footbed” or “sockliner”) or any other layers that faces to the wear’s foot when a wearer wears a shoe comprising the above- mentioned layers.
  • distal surface refers to the surface of the strobel board, outsole, insole or any other layers that faces to the ground.
  • heel region everything within the rear portion of the strobel is termed the heel region
  • everything within the frontal portion of the strobel is termed the front region.
  • the heel region preferably means the rear third of the strobel
  • the front region preferably means the frontal third of the strobel, in each case based on the length of the strobel; and the remaining middle third of the strobel is termed the midfoot region.
  • the strobel may have any shapes or configurations.
  • the following em bodiments are described to facilitate the understanding of the present invention, without any attempt to limit the scope thereof.
  • the strobel is ergonomically designed; in other word, it has a shape and configuration as commonly used in the footwear engineering field.
  • the strobel has a relatively uniform thickness in the intermediate region and similar thickness in the periphery region.
  • the strobel has a relatively uniform thickness in the intermediate region, and a thinner thickness in the periphery region.
  • the strobel has a gradually increased thickness from forefoot to heel.
  • the strobel has a forefoot region, a midfoot region, and a heel re gion, in which the strobel may define one or more thicker forefoot region(s) in the forefoot region and/or one or more thicker heel region(s) in the heel region on the distal surface.
  • the thicker region may be provided with any shape and size.
  • the thickness is 1-100 mm, preferably 5-50 mm, more preferably 10-30 mm, and even more preferably 10-25 mm.
  • the thickness in the intermediate region is 1-100 mm, prefera bly 5-50 mm, more preferably 10-30 mm, even more preferably 10-25 mm, and the thickness in the periphery region is 1-100 mm, preferably 5-50 mm, more preferably 10-30 mm, and even more preferably 10-25 mm.
  • the strobel may have a gradually increased thickness from the intermediate region to the periphery region, rather than form a fault between the intermediate region and the periphery region.
  • the strobel When the strobel has a gradually increased thickness from forefoot to heel, the strobel has a thickness of 1-100 mm, preferably 5-50 mm, more preferably 10-30 mm, and even more prefer ably 10-25 mm in the forefoot region, and a thickness of 2-100 mm, preferably 5-50 mm, more preferably 10-30 mm, even more preferably 10-25 mm in the heel region.
  • the strobel is optionally provided with a thin textile layer on the proximal surface of the strobel.
  • the thin textile layer may be selected from woven, non-woven, fabric.
  • the thin textile layer may have a thickness of 0.1 mm to 10 mm, preferably 0.5 mm to 4 mm, more preferably 1 mm to 3 mm.
  • the layer of thin textile provides the strobel with an anti-static property.
  • the layer of thin textile is provided to en hance the appearances of the strobel.
  • the layer of thin textile may be dispensed.
  • the present invention further provides an article of footwear, including a strobel as defined in the above.
  • the present invention further provides an article of footwear, including a strobel comprising ETPU or a hybrid material of ETPU and a PU foam matrix.
  • the article of footwear includes the strobel as defined in the above, an upper and an outsole. In an embodiment, the article of footwear comprises the strobel as defined in the above, an upper bottomed with the strobel, and an outsole disposed below the strobel.
  • the article of footwear comprises a strobel and an outsole in the shoe sole, and optionally any other possible layers.
  • the shoe sole assembly of the article of footwear consists of a strobel, an insole and an outsole.
  • the shoe sole assembly of the article of footwear consists of a strobel and an outsole.
  • a shoe sole assembly means all the parts that constitute a shoe sole.
  • an insole has a general meaning as understood by those skilled in the art, which often is posi tioned with the foot-receiving cavity in the upper above the strobel board.
  • the article of footwear is prepared by stitching the upper to the strobel. In an embodiment, the article of footwear is prepared by hot pressing the strobel to the outsole.
  • the outsole is made of any materials commonly used in the prior art, such as ethylene vinyl acetate (EVA), polyurethane (PU) or suitable rubbers.
  • EVA ethylene vinyl acetate
  • PU polyurethane
  • the outsole is made of TPU.
  • the strobel is processed to form a relatively thin periphery, and then the up- per is stitched to the thin periphery of the strobel.
  • the strobel has a shape of thin periphery, and the stitching may be achieved by threading the stitching line through the thin periphery.
  • the strobel has a thickness in the periphery region of 0.5-15 mm, preferably 2-10 mm, more preferably 2-5 mm.
  • the upper is stitched to the strobel by slotting the periphery of the strobel and stitching the upper to the strobel at the slotted periphery.
  • the strobel has relatively thick periphery region, and thus the strobel is cut open in the thickness direction to have a slot with certain depth.
  • the strobel has a thickness in the periphery region of 0.1-60 mm, preferably 0.2-50 mm, more preferably 1- 40 mm, even more preferably 1-30 mm and in particularly 2-15 mm.
  • the slot is distant in thickness direction from the proximal surface of the strobel by 0.1-10 mm, prefera bly 0.2-8 mm, more preferably 0.5-5 mm.
  • the stitching process itself is well known to those skilled in the art.
  • the hot press process itself is well known to those skilled in the art.
  • the hot press process is carried out before or after stitching the strobel to the upper.
  • the hot press process is performed at any temperatures suitable for the ma terials used. In an embodiment, the hot press process is performed at a temperature of 100- 200°C, preferably 120-190°C, more preferably 150-180°C, for about 0.5 min to 3 min, preferably 50 s to 2 min, more preferably 1 min to 1.5 min.
  • the article of footwear of the present invention possesses good properties in terms of cushioning and energy return, while still being light weight and highly durable.
  • the present invention further provides a process of manufacturing an article of footwear, com prising i) stitching an upper to one of the strobels as defined in the above; and/or ii) hot-pressing one of the strobels as defined in the above to an outsole.
  • step i) may be achieved by i-1) processing the strobel to form a relatively thin periphery and stitching the upper to the strobel at the thin periphery, or i-2) slotting the periphery of the strobel and stitching the strobel to the upper at the slotted pe riphery.
  • the processing step of i-1) is preferably performed in such a mold that the desired shape is directly obtained during the preparation of ETPU or the hybrid material of ETPU and a PU foam matrix.
  • the processing step of i-1) is performed by mechanically processing the strobel according to the invention to form the thin periphery.
  • the process of manufacturing an article of footwear further comprises a step of hot-pressing the strobel to the outsole.
  • the stitching, slotting and hot-pressing processes may have the same meaning as defined in the above.
  • step i) and ii) is interchangeable in the order.
  • step ii) may be performed be fore or after step i).
  • a strobel for an article of footwear wherein the strobel comprises ETPU.
  • component (b) is selected from polyether polyol, polyester polyol or mixtures thereof.
  • An article of footwear comprising a strobel as defined in any one of embodiments 1-15.
  • a process of manufacturing an article of footwear comprising: i) stitching an upper to the strobel as defined in any one of embodiments 1-15; and/or ii) hot-pressing the strobel as defined in any one of embodiments 1-15 to an outsole.
  • step i) comprises i-1) processing the strobel to form a relatively thin periphery and stitching the upper to the strobel at the thin periphery, or i-2) slotting the periphery of the strobel and stitching the strobel to the upper at the slotted periphery.
  • ETPU1 used was commercially available from BASF SE under the tradename of InfinergyTM, which has a bulk density of 200 kg/m 3 and has an average particle size of 3 mm.
  • ETPU2 used was commercially available from BASF SE under the tradename of InfinergyTM, which has a bulk density of 200 kg/m 3 and has an average particle size of 7 mm.
  • Prep 1 having an NCO content of 5% is prepared by reacting MDI with PO/EO based polyether polyol, defined as polyol 1 in the following.
  • Prep 2 having an NCO content of 19% is prepared by reacting MDI with PO/EO based polyether polyol, defined as polyol 2 in the following.
  • Chain extender monoethylene glycol (MEG)
  • Table 1 formulation of the PU foam matrix (% by weight)
  • Example 1-1 was produced using ETPU1 by steamchest molding process, wherein the process was performed at a temperature of about 110°C.
  • Example 1-2 and Example 1-3 were produced by similar process as described for Example 1-1. 2. Manufacturing process of the strobel with a hybrid material of ETPU and a PU foam matrix:
  • the ETPU beads were put into the container of low-pressure machine, and the PU raw materials were kept in the working temperature of about 55°C.
  • the ETPU beads and PU raw materials were pushed into the mixing head by screw and pump. Then all of them were poured into the steel mold. Then the PU started foaming and was covered with ETPU. After 2.5-4 min, the steel mold was opened to obtain the final strobel.
  • Examples 2-2, 2-3, 3-1, 3-2 and 3-3 were produced by similar process as described for Exam- pies 2-1.
  • Comparative example 1 was produced using wood paper, and has a thickness of 10 mm.
  • Table 2 preparation of different strobels and the mechanical properties of the same
  • the strobel has an ergonomically designed shape, which means a relatively thick por tion in heel region and a relatively thin portion in the front region.
  • the detailed shape refers to figures 1 and 2.
  • the thickness is measured according to the thickness of the main part of the strobel. For instance, example 1-1 having a thickness of 4 to 6 mm refers to that the strobel has an average thickness of about 6 mm in heel region and of about 4 mm in front re- gion.
  • the strobels were subjected to a stitch-tear strength test to determine their ability to hold stitch es according to SATRA TM5.
  • Comparative examples 2 and 3 were produced using PU foam and EVA foam, respectively.
  • EVA foam density 100 kg/m 3 ; thickness: 4 mm.
  • PU foam density 100 kg/m 3 ; thickness: 4 mm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un article chaussant et, plus particulièrement, un strobel pour un article chaussant, un article chaussant comprenant le strobel et également le procédé de fabrication de l'article chaussant.
EP22711529.2A 2021-03-12 2022-03-08 Strobel pour un article chaussant, article chaussant et procédé de fabrication de l'article chaussant Pending EP4304409A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2021080489 2021-03-12
PCT/EP2022/055927 WO2022189447A1 (fr) 2021-03-12 2022-03-08 Strobel pour un article chaussant, article chaussant et procédé de fabrication de l'article chaussant

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EP4304409A1 true EP4304409A1 (fr) 2024-01-17

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US (1) US20240148108A1 (fr)
EP (1) EP4304409A1 (fr)
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WO (1) WO2022189447A1 (fr)

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE111394C (fr)
US3304273A (en) 1963-02-06 1967-02-14 Stamberger Paul Method of preparing polyurethanes from liquid, stable, reactive, filmforming polymer/polyol mixtures formed by polymerizing an ethylenically unsaturated monomer in a polyol
GB1022434A (en) 1961-11-28 1966-03-16 Union Carbide Corp Improvements in and relating to polymers
US3523093A (en) 1961-11-28 1970-08-04 Paul Stamberger Method of producing polyurethanes by reacting polyisocyanate with a preformed polymer resulting from polymerization of ethylenically unsaturated monomers
DE1152536B (de) 1962-03-30 1963-08-08 Bayer Ag Verfahren zur Herstellung Urethangruppen enthaltender Schaumstoffe
DE1152537B (de) 1962-06-02 1963-08-08 Bayer Ag Verfahren zur Herstellung von homogenen, Urethangruppen aufweisenden Kunststoffen
ES8800697A1 (es) 1986-06-10 1987-12-01 Hoocker Sa Procedimiento para la obtencion de dispersiones de polimeros en poliesteres hidroxilados.
WO2005098763A2 (fr) 2004-04-06 2005-10-20 Giesecke & Devrient Gmbh Dispositif et procede pour traiter des billets de banque
ATE482991T1 (de) 2006-01-18 2010-10-15 Basf Se Schaumstoffe auf basis thermoplastischer polyurethane
PL2109637T3 (pl) 2007-01-16 2019-02-28 Basf Se Układy hybrydowe ze spienionych termoplastycznych elastomerów i poliuretanów
DE102013207156A1 (de) * 2013-04-19 2014-10-23 Adidas Ag Schuh, insbesondere ein Sportschuh
US20160302517A1 (en) 2015-04-17 2016-10-20 Wolverine World Wide, Inc. Sole assembly for an article of footwear
US20160302519A1 (en) * 2015-04-17 2016-10-20 Adidas Ag Article of Footwear Having a Midsole and Methods of Making the Same
TW201936684A (zh) * 2017-12-20 2019-09-16 德商巴斯夫歐洲公司 新穎彈性聚氨酯發泡材
CN112153915A (zh) 2018-05-30 2020-12-29 耐克创新有限合伙公司 鞋类物品和制造鞋类物品的方法
EP3886632B1 (fr) 2018-11-30 2023-11-22 NIKE Innovate C.V. Cousu strobel pour un article chaussant et procédé de fabrication

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WO2022189447A1 (fr) 2022-09-15
US20240148108A1 (en) 2024-05-09

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